Reaction product of a polar modified polymer and an alkoxysilane and a composition containing the reaction product

ABSTRACT

The invention relates to a reaction product of a polar modified polymer and an alkoxysilane having at least one solubilizing functional group and at least one amino substituent.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional application of U.S. Ser. No.12/982,108 filed Dec. 30, 2010, now allowed, the entire contents ofwhich is hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to a reaction product of a polar modifiedpolymer and an alkoxysilane having at least one solubilizing functionalgroup and at least one amino substituent, as well as a compositioncomprising the reaction product. The reaction product and compositioncontaining said reaction product have industrial, pharmacological and/orcosmetic applicability and can act as a carrier or matrix for desiredagents.

BACKGROUND OF THE INVENTION

It is desirable to formulate products and to make them available toconsumers in various forms such as in anhydrous, aqueous and emulsiontypes of compositions. It is also desirable that these products havelong wearing and transfer-resistant properties, that is, they adherelonger to surfaces and substrates such as keratinous materials. One wayof achieving these properties is through the use of film forming resinssuch as silicone film forming resins in anhydrous systems. However, onedrawback associated with their use is that they tend to be brittle andflake off.

Another way of achieving long wearing and transfer-resistant propertiesis to employ latex film-formers in oil-in-water emulsions which helpimprove the adhesion of the compositions to surfaces and keratinousmaterials. However, latex film formers can be difficult to formulatewith due to the large solid content load required, making them unstable,or sensitive to added ingredients. Moreover, the formulation ofemulsions which use traditional surfactants or emulsifying agents canpose challenges with respect to stability and effective delivery ofbeneficial ingredients or desired agents.

Thus, there remains a need for improved products which have long-wearingand transfer-resistant properties, which can be made available invarious types of compositions such as anhydrous, aqueous and emulsiontypes, and which can also function as a carrier and/or matrix fordesired agents.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a reaction product of at least onepolar modified polymer and at least one alkoxysilane having at least onesolubilizing functional group and at least one amino substituent.

The present invention also relates to compositions containing a reactionproduct of at least one polar modified polymer and at least onealkoxysilane having at least one solubilizing functional group and atleast one amino substituent; and at least one oil carrier.

The present invention also relates to methods of treating, caring forand/or making up keratinous material (for example, skin, hair, eyes,eyelashes, lips or hair) by applying the compositions of the presentinvention to the keratinous material in an amount sufficient to treat,care for and/or make up the keratinous material.

The present invention also relates to compositions containing at leastone polar modified polymer; at least one alkoxysilane having at leastone solubilizing functional group and at least one amino substituent; atleast one oil carrier; optionally, water; optionally, at least onedesired agent; and optionally, at least one auxiliary agent.

The present invention also relates to compositions as described abovewhich impart good adhesion, long-wear and/or transfer-resistanceproperties, as well as improved feel or texture properties to acomposition, such as a cosmetic composition, upon application to asurface or a keratinous material.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory only,and are not restrictive of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the expression “at least one” means one or more and thusincludes individual components as well as mixtures/combinations.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients and/or reaction conditionsare to be understood as being modified in all instances by the term“about,” meaning within 10% to 15% of the indicated number.

“Film former” or “film forming agent” as used herein means a polymer orresin that leaves a film on the substrate to which it is applied, forexample, after a solvent accompanying the film former has evaporated,absorbed into and/or dissipated on the substrate.

“Transfer resistance” as used herein refers to the quality exhibited bycompositions that are not readily removed by contact with anothermaterial, such as, for example, a glass, an item of clothing or theskin, for example, when eating or drinking. Transfer resistance may beevaluated by any method known in the art for evaluating such. Forexample, transfer resistance of a composition may be evaluated by a“kiss” test. The “kiss” test may involve application of the compositionto human keratin material such as hair, skin or lips followed by rubbinga material, for example, a sheet of paper, against the hair, skin orlips after expiration of a certain amount of time following application,such as 2 minutes after application. Similarly, transfer resistance of acomposition may be evaluated by the amount of product transferred from awearer to any other substrate, such as transfer from the hair, skin orlips of an individual to a collar when putting on clothing after theexpiration of a certain amount of time following application of thecomposition to the hair, skin or lips. The amount of compositiontransferred to the substrate (e.g., collar, or paper) may then beevaluated and compared. For example, a composition may be transferresistant if a majority of the product is left on the wearer's hair,skin or lips. Further, the amount transferred may be compared with thattransferred by other compositions, such as commercially availablecompositions. In a preferred embodiment of the present invention, littleor no composition is transferred to the substrate from the hair, skin orlips.

“Long wear” compositions as used herein, refers to compositions wherecolor remains the same or substantially the same as at the time ofapplication, as viewed by the naked eye, after an extended period oftime. Long wear properties may be evaluated by any method known in theart for evaluating such properties. For example, long wear may beevaluated by a test involving the application of a composition to humanhair, skin or lips and evaluating the color of the composition after anextended period of time. For example, the color of a composition may beevaluated immediately following application to hair, skin or lips andthese characteristics may then be re-evaluated and compared after acertain amount of time. Further, these characteristics may be evaluatedwith respect to other compositions, such as commercially availablecompositions.

“Tackiness” as used herein refers to the adhesion between twosubstances. For example, the more tackiness there is between twosubstances, the more adhesion there is between the substances. Toquantify “tackiness,” it is useful to determine the “work of adhesion”as defined by IUPAC associated with the two substances. Generallyspeaking, the work of adhesion measures the amount of work necessary toseparate two substances. Thus, the greater the work of adhesionassociated with two substances, the greater the adhesion there isbetween the substances, meaning the greater the tackiness is between thetwo substances.

Work of adhesion and, thus, tackiness, can be quantified usingacceptable techniques and methods generally used to measure adhesion,and is typically reported in units of force time (for example, gramseconds (“g s”)). For example, the TA-XT2 from Stable Micro Systems,Ltd. can be used to determine adhesion following the procedures setforth in the TA-XT2 Application Study (ref: MATI/PO.25), revised January2000, the entire contents of which are hereby incorporated by reference.According to this method, desirable values for work of adhesion forsubstantially non-tacky substances include less than about 0.5 g s, lessthan about 0.4 g s, less than about 0.3 g s and less than about 0.2 g s.As known in the art, other similar methods can be used on other similaranalytical devices to determine adhesion.

“Waterproof” as used herein refers to the ability to repel water andpermanence with respect to water. Waterproof properties may be evaluatedby any method known in the art for evaluating such properties. Forexample, a mascara composition may be applied to false eyelashes, whichmay then be placed in water for a certain amount of time, such as, forexample, 20 minutes. Upon expiration of the pre-ascertained amount oftime, the false eyelashes may be removed from the water and passed overa material, such as, for example, a sheet of paper. The extent ofresidue left on the material may then be evaluated and compared withother compositions, such as, for example, commercially availablecompositions. Similarly, for example, a composition may be applied toskin, and the skin may be submerged in water for a certain amount oftime. The amount of composition remaining on the skin after thepre-ascertained amount of time may then be evaluated and compared. Forexample, a composition may be waterproof if a majority of the product isleft on the wearer, e.g., eyelashes, skin, etc. In a preferredembodiment of the present invention, little or no composition istransferred from the wearer.

“Substituted” as used herein, means comprising at least one substituent.Non-limiting examples of substituents include atoms, such as oxygenatoms and nitrogen atoms, as well as functional groups, such as hydroxylgroups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylenegroups, polyoxyalkylene groups, carboxylic acid groups, amine groups,acylamino groups, amide groups, halogen containing groups, ester groups,thiol groups, sulphonate groups, thiosulphate groups, siloxane groups,and polysiloxane groups. The substituent(s) may be further substituted.

“Volatile”, as used herein, means having a flash point of less thanabout 100 degrees C.

“Non-volatile”, as used herein, means having a flash point of greaterthan about 100 degrees C.

The compositions and methods of the present invention can comprise,consist of, or consist essentially of the essential elements andlimitations of the invention described herein, as well as any additionalor optional ingredients, components, or limitations described herein orotherwise useful.

Polar Modified Polymer

According to the present invention, compositions comprising at least onepolar modified polymer are provided. “Polar modified polymer” as usedherein refers to “oil-soluble polar modified polymers” and/or“oil-soluble high carbon polar modified polymers.”

Oil-Soluble Polar Modified Polymer

According to the present invention, compositions comprising at least oneoil-soluble polar modified polymer are provided. “Polar modifiedpolymer” as used herein refers to a hydrophobic homopolymer or copolymerwhich has been modified with hydrophilic unit(s). “Oil-soluble” as usedherein means that the polar modified polymer is soluble in oil.

Suitable monomers for the hydrophobic homopolymers and/or copolymersinclude, but are not limited to, cyclic, linear or branched, substitutedor unsubstituted, C2-C20 compounds such as, for example, styrene,ethylene, propylene, isopropylene, butylene, isobutylene, pentene,isopentene, isoprene, hexene, isohexene, decene, isodecene, andoctadecene, including all ranges and subranges therebetween. Preferably,the monomers are C2-C8 compounds, more preferably C2-C6 compounds, andmost preferably C2-C4 compounds such as ethylene, propylene andbutylenes.

Suitable hydrophilic unit(s) include, but are not limited to, maleicanhydride, acrylates, alkyl acrylates such as, for example, methylacrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, andpolyvinylpyrrolidone (PVP).

According to the present invention, the polar modified polymer isoil-soluble: that is, the polymer does not contain a sufficient amountof hydrophilic unit(s) to render the entire polymer water-soluble oroil-insoluble. According to preferred embodiments, the polar modifiedpolymer contains the same amount of hydrophobic monomer as hydrophilicunit (1:1 ratio) or more hydrophobic monomer than hydrophilic unit.According to particularly preferred embodiments, the polar modifiedpolymer contains 50% or less hydrophilic unit(s) (based on weight of thepolymer), 40% or less hydrophilic unit(s), 30% or less hydrophilicunit(s), 20% or less hydrophilic unit(s), 10% or less hydrophilicunit(s), 5% or less hydrophilic unit(s), 4% or less hydrophilic unit(s),or 3% or less hydrophilic unit(s).

Preferably, the polar modified polymer has from about 0.5% to about 10%hydrophilic units, more preferably from about 1% to about 8% hydrophilicunits by weight with respect to the weight of the polymer, including allranges and subranges therebetween. Particularly preferredhydrophilically modified polymers are ethylene and/or propylenehomopolymers and copolymers which have been modified with maleicanhydride units.

According to preferred embodiments of the present invention, the polarmodified polymer is a wax. According to particularly preferredembodiments, the polar modified wax is made via metallocene catalysis,and includes polar groups or units as well as a hydrophobic backbone.Suitable modified waxes include those disclosed in U.S. patentapplication publication no. 20070031361, the entire contents of which ishereby incorporated by reference. Particularly preferred polar modifiedwaxes are C2-C3 polar modified waxes.

In accordance with preferred embodiments of the present invention, thepolar modified wax is based upon a homopolymer and/or copolymer wax ofhydrophobic monomers and has a weight-average molecular weight Mw ofless than or equal to 25 000 g/mol, preferably of 1000 to 22 000 g/moland particularly preferably of 4000 to 20,000 g/mol, a number-averagemolecular weight Mn of less than or equal to 15 000 g/mol, preferably of500 to 12 000 g/mol and particularly preferably of 1000 to 5000 g/mol, amolar mass distribution Mw/Mn in the range from 1.5 to 10, preferablyfrom 1.5 to 5, particularly preferably from 1.5 to 3 and especiallypreferably from 2 to 2.5, which have been obtained by metallocenecatalysis. Also, the polar modified wax preferably has a melting pointabove 75° C., more preferably above 90° C. such as, for example, amelting point between 90° C. and 160° C., preferably between 100° C. and150° C., including all ranges and subranges therebetween.

In the case of a copolymer wax, it is preferable to have, based on thetotal weight of the copolymer backbone, 0.1 to 30% by weight ofstructural units originating from the one monomer and 70.0 to 99.9% byweight of structural units originating from the other monomer. Suchhomopolymer and copolymer waxes can be made, for example, by the processdescribed in EP 571 882, the entire contents of which is herebyincorporated by reference, using the metallocene catalysts specifiedtherein. Suitable preparation processes include, for example, suspensionpolymerization, solution polymerization and gas-phase polymerization ofolefins in the presence of metallocene catalysts, with polymerization inthe monomers also being possible.

Polar modified waxes can be produced in a known manner from thehomopolymers and copolymers described above by oxidation withoxygen-containing gases, for example air, or by graft reaction withpolar monomers, for example maleic acid or acrylic acid or derivativesof these acids. The polar modification of metallocene polyolefin waxesby oxidation with air is described, for example, in EP 0 890 583 A1, andthe modification by grafting is described, for example, in U.S. Pat. No.5,998,547, the entire contents of both of which are hereby incorporatedby reference in their entirety.

Acceptable polar modified waxes include, but are not limited to,homopolymers and/or copolymers of ethylene and/or propylene groups whichhave been modified with hydrophilic units such as, for example, maleicanhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc.Preferably, the polar modified wax has from about 0.5% to about 10%hydrophilic units, more preferably from about 1% to about 8% hydrophilicunits by weight with respect to the weight of the wax, including allranges and subranges therebetween. Particularly preferredhydrophilically modified waxes are ethylene and/or propylenehomopolymers and copolymers which have been modified with maleicanhydride units.

Particularly preferred polar modified waxes for use in the presentinvention are C2-C3 polar modified waxes such as polypropylene and/orpolyethylene-maleic anhydride modified waxes (“PEMA,” “PPMA.” “PEPPMA”)commercially available from Clariant under the trade name LICOCARE orLICOCENE, Specific examples of such waxes include products marketed byClariant under the LicoCare name having designations such as PP207.

Other suitable polar modified polymers include, but are not limited toA-C 573 A (ETHYLENE-MALEIC ANHYDRIDE COPOLYMER; Drop Point, Mettler:106° C.) from Honeywell, A-C 596 A (PROPYLENE-MALEIC ANHYDRIDECOPOLYMER; Drop Point, Mettler: 143° C.) from Honeywell, A-C 597(PROPYLENE-MALEIC ANHYDRIDE COPOLYMER; Drop Point, Mettler: 141° C.)from Honeywell, ZeMac® copolymers (from VERTELLUS) which are 1:1copolymers of ethylene and maleic anhydride, polyisobutylene-maleicanhydride sold under the trade name ISOBAM (from Kuraray),polyisoprene-graft-maleic anhydride sold by Sigma Aldrich, poly(maleicanhydride-octadecene) sold by Chevron Philips Chemical Co.,poly(ethylene-co-butyl acrylate-co-maleic anhydride) sold under thetrade name of Lotader (e.g. 2210, 3210, 4210, and 3410 grades) byArkema, copolymers in which the butyl acrylate is replaced by otheralkyl acrylates (including methyl acrylate [grades 3430, 4404, and 4503]and ethyl acrylate [grades 6200, 8200, 3300, TX 8030, 7500, 5500, 4700,and 4720) also sold by Arkema under the Lotader name, and isobutylenemaleic anhydride copolymer sold under the name ACO-5013 by ISP.

Oil-Soluble High Carbon Polar Modified Polymer

According to the present invention, compositions comprising at least oneoil-soluble high carbon polar modified polymer are also provided. “Polarmodified polymer” as used herein refers to a hydrophobic homopolymer orcopolymer which has been modified with hydrophilic unit(s).“Oil-soluble” as used herein means that the polar modified polymer issoluble in oil. “High carbon” means more than 20 carbon atoms.

Suitable monomers for the hydrophobic homopolymers and/or copolymersinclude, but are not limited to, cyclic, linear or branched, substitutedor unsubstituted, C22-C40 compounds such as, C22-C28 compounds, C24-C26compounds, C26-C28 compounds, and C30-C38 compounds, including allranges and subranges therebetween. Preferably, the monomers are C24-26compounds, C26-C28 compounds or C30-C38 compounds.

Suitable hydrophilic unit(s) include, but are not limited to, maleicanhydride, acrylates, alkyl acrylates such as, for example, methylacrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, andpolyvinylpyrrolidone (PVP).

According to preferred embodiments, the oil-soluble high carbon polarmodified polymer is a wax. Also preferably, the oil-soluble high carbonpolar modified polymer wax has one or more of the following properties:

a weight-average molecular weight Mw of less than or equal to 30 000g/mol, preferably of 500 to 10 000 g/mol and particularly preferably of1000 to 5,000 g/mol, including all ranges and subranges therebetween;

a number-average molecular weight Mn of less than or equal to 15 000g/mol, preferably of 500 to 12 000 g/mol and particularly preferably of1000 to 5000 g/mol, including all ranges and subranges therebetween;

a molar mass distribution Mw/Mn in the range from 1.5 to 10, preferablyfrom 1.5 to 5, particularly preferably from 1.5 to 3 and especiallypreferably from 2 to 2.5, including all ranges and subrangestherebetween; and/or

a crystallinity of 8% to 60%, preferably 9% to 40%, and more preferably10% to 30%, including all ranges and subranges therebetween, asdetermined by differential scanning calorimetry.

According to preferred embodiments relating to a copolymer wax, it ispreferable to have, based on the total weight of the copolymer backbone,0.1 to 30% by weight of structural units originating from the onemonomer and 70.0 to 99.9% by weight of structural units originating fromthe other monomer.

Waxes of the present invention can be based upon homopolymers orcopolymers made, for example, by the process described in EP 571 882,the entire contents of which is hereby incorporated by reference.Suitable preparation processes include, for example, suspensionpolymerization, solution polymerization and gas-phase polymerization ofolefins in the presence of catalysts, with polymerization in themonomers also being possible.

Oil-soluble high carbon polar modified polymer wax can be produced in aknown manner from the homopolymers and copolymers described above byoxidation with oxygen-containing gases, for example air, or by graftreaction with polar monomers, for example maleic acid or acrylic acid orderivatives of these acids. The polar modification of polyolefin waxesby oxidation with air is described, for example, in EP 0 890 583 A1, andthe modification by grafting is described, for example, in U.S. Pat. No.5,998,547, the entire contents of both of which are hereby incorporatedby reference in their entirety.

Acceptable oil-soluble high carbon polar modified polymer waxes include,but are not limited to, homopolymers and/or copolymers of C24, C25and/or C26 groups, copolymers C26, C27 and/or C28 groups, or copolymersof C30-C38 groups, which have been modified with hydrophilic units suchas, for example, maleic anhydride, acrylate, methacrylate,polyvinylpyrrolidone (PVP), etc. Preferably, the oil-soluble high carbonpolar modified polymer wax has from about 5% to about 30% hydrophilicunits, more preferably from about 10% to about 25% hydrophilic units byweight with respect to the weight of the wax, including all ranges andsubranges therebetween. Particularly preferred hydrophilically modifiedwaxes are C26, C27 and/or C28 homopolymers and copolymers which havebeen modified with maleic anhydride units.

Particularly preferred oil-soluble high carbon polar modified polymerwaxes for use in the present invention are C26-C28 alpha olefin maleicacid anhydride copolymer waxes commercially available from Clariantunder the trade name LICOCARE or LICOCENE. Specific examples of suchwaxes include products marketed by Clariant under the LicoCare namehaving designations such as CM 401, which is a maleic anhydride modifiedwax having a Mw of 2025 and a crystallinity of 11%, C30-C38olefin/isopropylmaleate/maleic anhydride copolymer sold by Baker Hughesunder the name Performa® V 1608, and C24-C26 alpha olefin acrylatecopolymer wax commercially available from Clariant under the trade nameLICOCARE CA301 LP3346 based on a polar backbone with C24-26 side chainswith alternating ester and carboxylic acid groups.

According to other embodiments of the present invention, the polarmodified polymer is not a wax. In accordance with these embodiments ofthe present invention, the polar modified polymer is based upon ahomopolymer and/or copolymer of hydrophobic monomer(s) and has aweight-average molecular weight Mw of less than or equal to 1,000,000g/mol, preferably of 1000 to 250,000 g/mol and particularly preferablyof 5,000 to 50,000 g/mol, including all ranges and subrangestherebetween.

In accordance with these embodiments, the polar modified polymer can beof any form typically associated with polymers such as, for example,block copolymer, a grafted copolymer or an alternating copolymer. Forexample, the polar modified polymer can contain a hydrophobic backbone(such as polypropylene and/or polyethylene) onto which hydrophilicgroups (such as maleic anhydride) have been attached by any meansincluding, for example, grafting. The attached groups can have anyorientation (for example, atactic, isotactic or syndiotactic along thebackbone).

Preferably, the polar modified polymer(s) of the present inventionrepresent from about 1% to about 30% by weight, more preferably fromabout 3% to about 25% by weight, and most preferably from about 5% toabout 20% by weight, of the total weight of the composition, includingall ranges and subranges therebetween.

Alkoxysilane

In accordance with the present invention, the alkoxysilane having atleast one solubilizing functional group and an amino substituent has anamine group available to react with hydrophilic groups on the backboneof the polar modified polymer.

As used herein, the term “at least one solubilizing functional group”means any functional chemical group facilitating the bringing intosolution of the alkoxysilane in the solvent or in a combination ofsolvents of the composition, for example, in solvents chosen from water,water-alcoholic mixtures, organic solvents, polar solvents and non-polarsolvents.

Suitable solubilizing functional groups for use in accordance with thepresent disclosure include, but are not limited to, primary, secondary,and tertiary amine, aromatic amine, alcohol, carboxylic acid, sulfonicacid, anhydride, carbamate, urea, guanidine, aldehyde, ester, amide,epoxy, pyrrole, dihydroimidazole, gluconamide, pyridyl, and polyethergroups.

The at least one alkoxysilane present in the composition comprises atleast one solubilizing functional group, which may be identical ordifferent, such as those previously defined.

The at least one alkoxysilane having at least one solubilizingfunctional group and amino substituent present in the composition of thepresent disclosure may comprise at least one silicon atom, for example,one silicon atom.

The at least one alkoxysilane having at least one solubilizingfunctional group and amino substituent present in the composition may,in at least one embodiment, comprise two or three alkoxy functions. Inanother embodiment, the alkoxy functional groups are chosen from methoxyand ethoxy functional groups.

According to one embodiment, the at least one alkoxysilane having atleast one solubilizing functional group and amino substituent present inthe composition of the present disclosure is chosen from compounds offormula (I):

wherein:

R₄ is chosen from OR′ groups;

R₅ is chosen from OR″ groups;

R₆ is chosen from OR′″ groups;

R₁, R₂ are chosen from hydrogen;

R₃, R′, R″, R′″, which may be identical or different, are chosen fromlinear and branched, saturated and unsaturated hydrocarbon groups,optionally bearing at least one additional chemical group, wherein R′,R″, and R′″ may also be chosen from hydrogen.

In at least one embodiment, the R′, R″, and R′″ groups are chosen fromC₁-C₁₂ alkyl, C₆-C₁₄ aryl, C₁-C₈ alkyl-C₆-C₁₄ aryl, and C₆-C₁₄aryl-C₁-C₈-alkyl radicals.

Particularly preferred alkoxysilanes having at least one solubilizingfunctional group and at least one amino substituent includealkoxysilanes comprising a silicone atom. Suitable examples includethose of formula R(4-n)SiXn, wherein X is a hydrolysable group such asmethoxy, ethoxy or 2 methoxyethoxy, R is a monovalent organic radicalwhich contains 1 to 12 carbon atoms and may contain groups such asmercapto, epoxy, acrylyl, methacrylyl, amino or urea, and n is aninteger from 1 to 4, and according to at least one embodiment is 3.Possible examples of useful alkoxysilanes include3-mercaptopropyltriethoxysilane and aminoalkyltrialkoxysilanes such as3-aminopropyltriethoxysilane, as described in French Patent ApplicationNo. FR 2 789 896.

In another embodiment, the useful alkoxysilanes of the present inventionmay be alkoxysilanes which carry a group having a cosmetic functionalgroup, such as aromatic nitro dyes or anthraquinone, napthoquinone,benzoquinone, azo, xanthene, triarylmethane, azine, indoaniline,indophenolic or indoamine dyes; groups having a reductive effect, suchas thiol groups, sulphinic acid or sulphinic salt, it being possible forthese alkoxysilanes to carry a solubilizing non-hydrolysable group suchas amino groups, carboxylic acids, sulphonic acids, sulphates,quaternary ammoniums, polyalcohols, polyether and phosphates. Onepossible example includesaminopropyl-N-(4,2-dinitrophenyl)aminopropyldiethoxysilane. Compounds ofthis kind are described, for example, in Patent Application EP 1 216023.

The alkoxysilanes of the present disclosure may be amino arylalkoxysilanes. Possible examples include but are not limited to thefollowing compounds:

3-(m-aminophenoxy)propyltrimethoxysilane, of the formula:

provided by GELEST,

p-aminophenyltrimethoxysilane, of formula:

provided by GELEST, and

N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane, of the formula:

provided by GELEST.

In another embodiment the at least one alkoxysilane having at least onesolubilizing functional group and at least one amino substituent is atrialkoxysilane.

In a preferred embodiment, the at least one alkoxysilane having at leastone solubilizing functional group and at least one amino substituentpresent in the composition of the present disclosure is aγ-aminopropyltriethoxysilane, also known as3-aminopropyltriethoxysilane.

The at least one alkoxysilane having at least one solubilizingfunctional group and at least one amino substituent of the presentinvention is soluble in both oil and water.

The at least one alkoxysilane having at least one solubilizingfunctional group and at least one amino substituent is employed in thecomposition of the invention in an amount ranging from about 0.01 toabout 10% by weight, such as from about 0.01 to about 5%, such as fromabout 0.05 to about 3% by weight, and from about 0.1 to about 2% byweight, based on the total weight of the composition, including allranges and subranges therebetween.

Reaction Product

Although not wanting to be bound by any particular theory, it isbelieved that the polar modified polymer reacts with the alkoxysilanehaving at least one solubilizing functional group and at least one aminosubstituent to form links or bonds between the amine groups of thealkoxysilane and the hydrophilic groups of the polar modified polymer.The appropriate amount of the alkoxysilane having at least onesolubilizing functional group and at least one amino substituent toreact with the polar modified polymer to obtain a reaction product canbe easily determined, taking into account the number/amount of reactiveamine groups on the alkoxysilane having at least one solubilizingfunctional group and at least one amino substituent and thenumber/amount of corresponding reactive groups on the polar modifiedpolymer (for example, maleic anhydride groups). According to preferredembodiments, excess polar modified polymer (as determined by therelative number/amount of corresponding reactive groups on the polymeras compared to the reactive amine group(s) on the alkoxysilane) isreacted with the alkoxysilane having at least one solubilizingfunctional group and at least one amino substituent. The molar ratio ofthe alkoxysilane having at least one solubilizing functional group andat least one amino substituent to polar modified polymer may range frombetween 0.003 and 6, such as between 0.01 and 1.5, and such as between0.1 and 0.5, including all ranges and subranges therebetween.

According to the present invention, any suitable amine chemistry can beused to form the reaction product of the present invention. The exactchemistry will depend upon the nature of the corresponding reactivegroup of the polar modified polymer with which the amine groups of thealkoxysilane having at least one solubilizing functional group and atleast one amino substituent will react. However, once the nature of thecorresponding reactive groups is known, their reaction with the aminegroups will proceed according to known amine chemistry principles.

According to preferred embodiments, the polar modified polymer isinitially present in an oil carrier, and the alkoxysilane having atleast one solubilizing functional group and at least one aminosubstituent is blended into the oil carrier during production of thecompositions of the present invention. Because the polar modifiedpolymer is typically solid at room temperature, the oil carriercontaining the polar modified polymer is preferably heated to liquefythe wax prior to combination with the alkoxysilane having at least onesolubilizing functional group and at least one amino substituent.Preferably, the oil carrier is heated beyond the melting point of thepolar modified polymer, typically up to about 70° C., 80° C., 90° C.,100° C. or 110° C. Then, the polar modified polymer is preferablycombined with the alkoxysilane having at least one solubilizingfunctional group and at least one amino substituent through blending atroom temperature or at an elevated temperature (that is, at atemperature between room temperature and the temperature at which thepolar modified wax was liquefied or melted or at a higher temperature)such as, for example, about 30° C., 40° C., 50° C., 60° C., 70° C., 80°C., 90° C., 120° C. or above 120° C. for at least about 1 minute,preferably at least about 5 minutes, preferably at least about 30minutes, including all time intervals therein.

According to preferred embodiments of the present invention, thecombination of the polar modified polymer and the alkoxysilane having atleast one solubilizing functional group and at least one aminosubstituent in one or more oil carriers can comprise an anhydrouscomposition. Preferably, the molar ratio of the alkoxysilane having atleast one solubilizing functional group and at least one aminosubstituent to polar modified polymer in an anhydrous composition mayrange from between 0.003 and 1, preferably from between 0.01 and 0.6,and preferably from between 0.1 and 0.4, including all ranges andsubranges therebetween.

According to other preferred embodiments of the present invention, thealkoxysilane having at least one solubilizing functional group and atleast one amino substituent is initially present in a water carrier inwhich the alkoxysilane undergoes hydrolysis and condensation to form apolyamine. The polar modified polymer is then combined with thealkoxysilane which is now in the form of a polyamine by combining thepolar modified polymer's oil carrier and the alkoxysilane's watercarrier. Although not wanting to be bound by any particular theory, itis believed that an emulsion constituting an oil phase and a water phaseis thus formed from the combination of the oil carrier and the watercarrier and that a reaction between the polar modified polymer and theamino group(s) on the alkoxysilane can occur at the oil-water interfaceof the emulsion.

According to another preferred embodiment of the present invention, thepolar modified polymer is initially present in an oil carrier and thealkoxysilane having at least one solubilizing functional group and atleast one amino substituent is initially present with both the polarmodified polymer in the oil carrier and in a separate water carrier.Although not wanting to be bound to any particular theory, it isbelieved in this case, that the polar modified polymer will first reactwith the alkoxysilane having at least one solubilizing functional groupand at least one amino substituent present in the oil carrier afterwhich any unreacted hydrophilic groups on the polar modified polymer canthen react with the amino group(s) of the condensation product of thealkoxysilane present in the water phase and/or with the ethoxy groups onthe alkoxysilane in the oil carrier with any free hydroxyl groups on thealkoxysilane in the water carrier at the oil-water interface of theemulsion formed between the oil carrier and the water carrier.Preferably, the molar ratio of the alkoxysilane having at least onesolubilizing functional group and at least one amino substituent topolar modified polymer in an emulsion composition may range from between0.003 and 6, preferably from between 0.01 and 3.5, and preferably frombetween 0.1 and 0.5, including all ranges and subranges therebetween.

According to other embodiments, the polar modified polymer and thealkoxysilane having at least one solubilizing functional group and atleast one amino substituent can be added to the oil carrier first, andthen the water can be subsequently added to the mixture to form anemulsion. Preferably, the molar ratio of the alkoxysilane having atleast one solubilizing functional group and at least one aminosubstituent to polar modified polymer is between 0.003 and 0.15,preferably between 0.005 and 0.13, and preferably between 0.01 and 0.05,including all ranges and subranges therebetween.

Without intending to be bound by any particular theory, it is believedthat due to the chemical and physical reactions which take place whenthe polar modified polymer is combined with the alkoxysilane having atleast one solubilizing functional group and at least one aminosubstituent, the subsequent reaction product or composition that isformed is surprisingly and unexpectedly able to entrap large amounts ofwater molecules within its hydrophobic matrix. The resultant product orcomposition resulting from the chemical and physical reactions betweenthe polar modified polymer and the alkoxysilane having at least onesolubilizing functional group and at least one amino substituent iscapable of forming a film, is self-emulsifying, and transfer-resistant.Moreover, the product or composition is both stable and capable ofcarrying various types of ingredients.

According to preferred embodiments, the oil carrier comprises volatileand/or non-volatile oils. Such oils can be any acceptable oil includingbut not limited to silicone oils and/or hydrocarbon oils.

According to preferred embodiments, the oil carrier comprises one ormore volatile silicone oils. Examples of such volatile silicone oilsinclude linear or cyclic silicone oils having a viscosity at roomtemperature less than or equal to 6 cSt and having from 2 to 7 siliconatoms, these silicones being optionally substituted with alkyl or alkoxygroups of 1 to 10 carbon atoms. Specific oils that may be used in theinvention include octamethyltetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane,hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxaneand their mixtures. Other volatile oils which may be used include KF 96Aof 6 cSt viscosity, a commercial product from Shin Etsu having a flashpoint of 94° C. Preferably, the volatile silicone oils have a flashpoint of at least 40° C.

Non-limiting examples of volatile silicone oils are listed in Table 1below.

TABLE 1 Flash Point Viscosity Compound (° C.) (cSt) Octyltrimethicone 931.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2(cyclopentasiloxane or D5) Octamethylcyclotetrasiloxane 55 2.5(cyclotetradimethylsiloxane or D4) Dodecamethylcyclohexasiloxane (D6) 937 Decamethyltetrasiloxane (L4) 63 1.7 KF-96 A from Shin Etsu 94 6 PDMS(polydimethylsiloxane) DC 200 56 1.5 (1.5 cSt) from Dow Corning PDMS DC200 (2 cSt) from Dow 87 2 Corning

Further, a volatile linear silicone oil may be employed in the presentinvention. Suitable volatile linear silicone oils include thosedescribed in U.S. Pat. No. 6,338,839 and WO03/042221, the contents ofwhich are incorporated herein by reference. In one embodiment thevolatile linear silicone oil is decamethyltetrasiloxane. In anotherembodiment, the decamethyltetrasiloxane is further combined with anothersolvent that is more volatile than decamethyltetrasiloxane.

According to other preferred embodiments, the oil carrier comprises oneor more non-silicone volatile oils and may be selected from volatilehydrocarbon oils, volatile esters and volatile ethers. Examples of suchvolatile non-silicone oils include, but are not limited to, volatilehydrocarbon oils having from 8 to 16 carbon atoms and their mixtures andin particular branched C₈ to C₁₆ alkanes such as C₈ to C₁₆ isoalkanes(also known as isoparaffins), isododecane, isodecane, and for example,the oils sold under the trade names of Isopar or Permethyl. Preferably,the volatile non-silicone oils have a flash point of at least 40° C.

Non-limiting examples of volatile non-silicone volatile oils are givenin Table 2 below.

TABLE 2 Compound Flash Point (° C.) Isododecane 43 Propylene glycoln-butyl ether 60 Ethyl 3-ethoxypropionate 58 Propylene glycolmethylether acetate 46 Isopar L (isoparaffin C₁₁-C₁₃) 62 Isopar H(isoparaffin C₁₁-C₁₂) 56

The volatility of the solvents/oils can be determined using theevaporation speed as set forth in U.S. Pat. No. 6,338,839, the contentsof which are incorporated by reference herein.

According to preferred embodiments of the present invention, the oilcarrier comprises at least one non-volatile oil. Examples ofnon-volatile oils that may be used in the present invention include, butare not limited to, polar oils such as:

-   -   hydrocarbon-based plant oils with a high triglyceride content        consisting of fatty acid esters of glycerol, the fatty acids of        which may have varied chain lengths, these chains possibly being        linear or branched, and saturated or unsaturated; these oils are        especially wheat germ oil, corn oil, sunflower oil, karite        butter, castor oil, sweet almond oil, macadamia oil, apricot        oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil,        poppy oil, pumpkin oil, sesame seed oil, marrow oil, avocado        oil, hazelnut oil, grape seed oil, blackcurrant seed oil,        evening primrose oil, millet oil, barley oil, quinoa oil, olive        oil, rye oil, safflower oil, candlenut oil, passion flower oil        or musk rose oil; or caprylic/capric acid triglycerides, for        instance those sold by the company Stearineries Dubois or those        sold under the names Miglyol 810, 812 and 818 by the company        Dynamit Nobel;    -   synthetic oils or esters of formula R₅COOR₆ in which R₅        represents a linear or branched higher fatty acid residue        containing from 1 to 40 carbon atoms, including from 7 to 19        carbon atoms, and R₆ represents a branched hydrocarbon-based        chain containing from 1 to 40 carbon atoms, including from 3 to        20 carbon atoms, and also including, for example, octyldodecyl        neopentanoate, Purcellin oil (cetostearyl octanoate), isononyl        isononanoate, C₁₂ to C₁₅ alkyl benzoate, isopropyl myristate,        2-ethylhexyl palmitate, and octanoates, decanoates or        ricinoleates of alcohols or of polyalcohols; hydroxylated        esters, for instance isostearyl lactate or diisostearyl malate;        and pentaerythritol esters;    -   synthetic ethers containing from 10 to 40 carbon atoms;    -   C₈ to C₂₆ fatty alcohols, for instance oleyl alcohol; and    -   mixtures thereof.

Further, examples of non-volatile oils that may be used in the presentinvention include, but are not limited to, non-polar oils such asbranched and unbranched hydrocarbons and hydrocarbon waxes includingpolyolefins, in particular Vaseline (petrolatum), paraffin oil,squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene,polybutene, mineral oil, pentahydrosqualene, and mixtures thereof.

The oil carrier of the present invention is employed in the compositionof the invention in an amount ranging from about 1 to about 90% byweight, more preferably from about 10% to about 85%, and more preferablyfrom about 40% to about 80% by weight, based on the total weight of thecomposition, including all ranges and subranges therebetween.

According to preferred embodiments of the present invention, the oilcarrier, the water carrier, or both comprise a desired agent to beincorporated within the reaction product or the compositions of thepresent invention. The desired agent can be, for example, any colorant(pigment, dye, etc.), any pharmaceutically or cosmetically active agent,or any film forming agent known in the art. Such a desired agent can beincorporated into the reaction product or into the compositions of thepresent invention. When the desired agent is incorporated into thereaction product, it can be active during subsequent use of acomposition comprising the reaction product. For example, a cosmeticmakeup composition or a paint composition comprising colorants withinthe reaction product can provide colorant and/or film forming agent to asubstrate (skin, lips, wall, frame, etc.) during use to provide thesubstrate with the desired film and/or color. Similarly, apharmaceutical or cosmetic composition comprising a pharmaceuticallyactive agent or a skin active agent can provide such active agent to thepatient or consumer upon use (for example, a transdermal patchcontaining the reaction product of the present invention within which isa pharmaceutically or cosmetically active agent, or a tablet or capsulecontaining the same reaction product/active agent combination).

Acceptable colorants include pigments, dyes, such as liposoluble dyes,nacreous pigments, and pearling agents.

Representative liposoluble dyes which may be used according to thepresent invention include Sudan Red, DC Red 17, DC Green 6, β-carotene,soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5,annatto, and quinoline yellow.

Representative nacreous pigments include white nacreous pigments such asmica coated with titanium or with bismuth oxychloride, colored nacreouspigments such as titanium mica with iron oxides, titanium mica withferric blue or chromium oxide, titanium mica with an organic pigmentchosen from those mentioned above, and nacreous pigments based onbismuth oxychloride.

Representative pigments include white, colored, inorganic, organic,polymeric, nonpolymeric, coated and uncoated pigments. Representativeexamples of mineral pigments include titanium dioxide, optionallysurface-treated, zirconium oxide, zinc oxide, cerium oxide, iron oxides,chromium oxides, manganese violet, ultramarine blue, chromium hydrate,and ferric blue. Representative examples of organic pigments includecarbon black, pigments of D & C type, and lakes based on cochinealcarmine, barium.

Representative cosmetically active agents include, but are not limitedto agents for combating free radicals, UV screening agents, moisturizingagents, and humectants. In the event that water or an aqueous carrier isemployed in the composition of the present invention, suitable examplesof moisturizing agents are, but not limited to, polyols such as glycerinand glycosaminoglycans (GAGS). GAgS are also referred to as acidicmucopolysaccharides on account of their high water-retaining capacity,their carbohydrate nature and their acidic nature derived from thenumerous negative charges thereon. The strong anionic nature of GAGS isexplained by the presence of carboxylate groups.

Suitable examples of glycosaminoglycans are hyaluronic acid orhyaluronan (HA), heparan sulfate (HS), heparin (HP), chondroitin,chondroitin sulfate (CS), chondroitin 4-sulfate or chondroitin sulfate A(CSA), chondroitin 6-sulfate or chondroitin sulfate C (CSC), dermatansulfate or chondroitin sulfate B (CSB) and keratan sulfate (KS).

In one preferred embodiment of the present invention, theglycosaminoglycan is chosen from hyaluronic acid, its derivatives andits salts. In the context of the present invention, the term “hyaluronicacid or a derivative thereof/” covers the basic unit of hyaluronic acidwhich includes the smallest fraction of hyaluronic acid comprising adisaccharide dimer, namely D-glucuronic acid and N-acetylglucosamine.

The term “hyaluronic acid or a derivative thereof” also comprises, inthe context of the present invention, the linear polymer comprising thepolymeric unit described above, linked together in the chain viaalternating beta(1,4) and beta(1,3) glycosidic linkages, having amolecular weight (MW) that can range between 380 and 13,000,000 daltons(Da). This molecular weight depends in large part on the source fromwhich the hyaluronic acid is obtained and/or on the preparation methods.

The term “hyaluronic acid or a derivative thereof” also comprises, inthe context of the present invention, the hyaluronic acid salts, and inparticular the alkali metals salts such as the sodium salt and thepotassium salt.

In the natural state, hyaluronic acid is present in pericellular gels,in the base substance of the connective tissues of vertebrate organssuch as the dermis and epithelial tissues, and in particular in theepidermis, in the synovial fluid of the joints, in the vitreous humor,in the human umbilical cord and in the crista galli apophysis.

Thus, the term “hyaluronic acid or a derivative thereof” comprises allthe fractions or subunits of hyaluronic acid having a molecular weightin particular within the molecular weight range recalled above.

According to a preferred embodiment of the invention the hyaluronic acidfractions suitable for the use covered by the present invention have amolecular weight of between 50,000 and 5,000,000, in particular between100,000 and 5,000,000, especially between 400,000 and 5,000,000 Da. Inthis case, the term used is high-molecular-weight hyaluronic acid.

Alternatively, the hyaluronic acid fractions that may also be suitablefor the use in the present invention are chosen from those with amolecular weight of between 50,000 and 400,000 Da(intermediate-molecular-weight hyaluronic acid) and from those with amolecular weight of less than 50,000 Da (low-molecular-weight hyaluronicacid).

Finally, the term “hyaluronic acid or a derivative thereof” alsocomprises hyaluronic acid esters in particular those in which all orsome of the carboxylic groups of the acid functions are esterified withoxyethylenated alkyls or alcohols, containing from 1 to 20 carbon atoms,in particular with a degree of substitution at the level of theD-glucuronic acid of the hyaluronic acid ranging from 0.5 to 50 percent.Mention may in particular be made of methyl, ethyl, n-propyl, n-pentyl,benzyl and dodecyl esters of hyaluronic acid.

The molecular weights indicated above are also valid for the hyaluronicacid esters.

Hyaluronic acid may in particular be hyaluronic acid supplied by thecompany Hyactive under the trade name CPN (MW: 10 to 150 kDa), by thecompany Soliance under the trade name Cristalhyal (MW: 1.1 million Da),by the company Bioland under the name Nutra HA (MW: 820,000 Da), by thecompany Bioland under the name Nutra AF (MW: 69,000 Da, by the companyBioland under the name Oligo HA (MW: 6100 Da) or else by the company VamFarmacos Metica under the name D Factor (MW: 380 Da).

In one embodiment, the hyaluronic acid is present in the form ofspheres. In particular, such spheres are sold by the company BASF underthe name Sphere d'Acide Hyaluronique [hyaluronic acid sphere]. It is amixture of hyaluronic acid of various molecular weights, i.e. of MW 1.5million, 400,000 and 600,000 Da.

The preferred form of hyaluronic acid in the present invention is sodiumhyaluronate, which is commercially available from Soliance in threedifferent forms produced from the fermentation of lactic bacteria on aplant substrate and known under the tradenames Bashyal, Vitalhyal andCristalhyal, whose molecular weights range from less than 0.2 million Dato more than 1 million Da.

Preferably, hyaluronic acid is employed in the reaction product and inthe compositions of the present invention in an amount of from about0.01% to about 5% by weight, more preferably, from about 0.2% to about2.0% by weight, and more preferably, from about 0.5% to about 1.5% byweight with respect to the total weight of the reactionproduct/composition, including all ranges and subranges therebetween.

Acceptable film forming agents and/or rheological agents are known inthe art and include, but are not limited to, those disclosed in U.S.patent application publication no. 2004/0170586, the entire contents ofwhich is hereby incorporated by reference.

Non-limiting representative examples of acceptable filmforming/rheolgocial agents include silicone resins such as, for example,MQ resins (for example, trimethylsiloxysilicates), T-propylsilsesquioxanes and MK resins (for example, polymethylsilsesquioxanes),silicone esters such as those disclosed in U.S. Pat. Nos. 6,045,782,5,334,737, and 4,725,658, the disclosures of which are herebyincorporated by reference, polymers comprising a backbone chosen fromaqueous polyurethane dispersions, vinyl polymers, methacrylic polymers,and acrylic polymers and at least one chain chosen from pendant siloxanegroups and pendant fluorochemical groups such as those disclosed in U.S.Pat. Nos. 5,209,924, 4,693,935, 4,981,903, 4,981,902, and 4,972,037, andWO 01/32737, the disclosures of which are hereby incorporated byreference, polymers such as those described in U.S. Pat. No. 5,468,477,the disclosure of which is hereby incorporated by reference (anon-limiting example of such polymers ispoly(dimethylsiloxane)-g-poly(isobutyl methacrylate), which iscommercially available from 3M Company under the tradename VS 70 IBM).

Suitable examples of acceptable liposoluble polymers include, but arenot limited to, polyalkylenes, polyvinylpyrrolidone (PVP) orvinylpyrrolidone (VP) homopolymers or copolymers, copolymers of a C₂ toC₃₀, such as C₃ to C₂₂ alkene, and combinations thereof. As specificexamples of VP copolymers which can be used in the invention, mentionmay be made of VP/vinyl acetate, VP/ethyl methacrylate, butylatedpolyvinylpyrrolidone (PVP), VP/ethyl methacrylate/methacrylic acid,VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylicacid/lauryl methacrylate copolymer.

One type of block copolymer which may be employed in the compositions ofthe present invention is a thermoplastic elastomer. The hard segments ofthe thermoplastic elastomer typically comprise vinyl monomers in varyingamounts. Examples of suitable vinyl monomers include, but are notlimited to, styrene, methacrylate, acrylate, vinyl ester, vinyl ether,vinyl acetate, and the like.

The soft segments of the thermoplastic elastomer typically compriseolefin polymers and/or copolymers which may be saturated, unsaturated,or combinations thereof. Suitable olefin copolymers may include, but arenot limited to, ethylene/propylene copolymers, ethylene/butylenecopolymers, propylene/butylene copolymers, polybutylene, polyisoprene,polymers of hydrogenated butanes and isoprenes, and mixtures thereof.

Thermoplastic elastomers useful in the present invention include blockcopolymers e.g., di-block, tri-block, multi-block, radial and star blockcopolymers, and mixtures and blends thereof. A di-block thermoplasticelastomer is usually defined as an A-B type or a hard segment (A)followed by a soft segment (B) in sequence. A tri-block is usuallydefined as an A-B-A type copolymer or a ratio of one hard, one soft, andone hard segment. Multi-block or radial block or star blockthermoplastic elastomers usually contain any combination of hard andsoft segments, provided that the elastomers possess both hard and softcharacteristics.

In preferred embodiments, the thermoplastic elastomer of the presentinvention may be chosen from the class of Kraton™ rubbers (ShellChemical Company) or from similar thermoplastic elastomers. Kraton™rubbers are thermoplastic elastomers in which the polymer chainscomprise a di-block, tri-block, multi-block or radial or star blockconfiguration or numerous mixtures thereof. The Kraton™ tri-blockrubbers have polystyrene (hard) segments on each end of a rubber (soft)segment, while the Kraton™ di-block rubbers have a polystyrene (hard)segment attached to a rubber (soft) segment. The Kraton™ radial or starconfiguration may be a four-point or other multipoint star made ofrubber with a polystyrene segment attached to each end of a rubbersegment. The configuration of each of the Kraton™ rubbers forms separatepolystyrene and rubber domains.

Each molecule of Kraton™ rubber is said to comprise block segments ofstyrene monomer units and rubber monomer and/or co-monomer units. Themost common structure for the Kraton™ triblock copolymer is the linearA-B-A block type styrene-butadiene-styrene, styrene-isoprene-styrene,styrene-ethylenepropylene-styrene, or styrene-ethylenebutylene-styrene.The Kraton™ di-block is preferably the AB block type such asstyrene-ethylenepropylene, styrene-ethylenebutylene, styrene-butadiene,or styrene-isoprene. The Kraton™ rubber configuration is well known inthe art and any block copolymer elastomer with a similar configurationis within the practice of the invention. Other block copolymers are soldunder the tradename Septon (which represent elastomers known as SEEPS,sold by Kurary, Co., Ltd) and those sold by Exxon Dow under thetradename Vector™

Other thermoplastic elastomers useful in the present invention includethose block copolymer elastomers comprising astyrene-butylene/ethylene-styrene copolymer (tri-block), anethylene/propylene-styrene copolymer (radial or star block) or a mixtureor blend of the two. (Some manufacturers refer to block copolymers ashydrogenated block copolymers, e.g. hydrogenatedstyrene-butylene/ethylene-styrene copolymer (tri-block)).

Acceptable film forming/rheological agents also include water solublepolymers such as, for example, high molecular weight crosslinkedhomopolymers of acrylic acid, and Acrylates/C10-30 Alkyl AcrylateCrosspolymer, such as the Carbopol® and Pemulen®; anionic acrylatepolymers such as Salcare® AST and cationic acrylate polymers such asSalcare® SC96; acrylamidopropylttrimonium chloride/acrylamide;hydroxyethyl methacrylate polymers, Steareth-10 Allyl Ether/AcrylateCopolymer; Acrylates/Beheneth-25 Metacrylate Copolymer, known as Aculyn®28; glyceryl polymethacrylate, Acrylates/Steareth-20 MethacrylateCopolymer; bentonite; gums such as alginates, carageenans, gum acacia,gum arabic, gum ghatti, gum karaya, gum tragacanth, guar gum; guarhydroxypropyltrimonium chloride, xanthan gum or gellan gum; cellulosederivatives such as sodium carboxymethyl cellulose, hydroxyethylcellulose, hydroxymethyl carboxyethyl cellulose, hydroxymethylcarboxypropyl cellulose, ethyl cellulose, sulfated cellulose,hydroxypropyl cellulose, methyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose; agar; pectin; gelatin; starch andits derivatives; chitosan and its derivatives such as hydroxyethylchitosan; polyvinyl alcohol, PVM/MA copolymer, PVM/MA decadienecrosspolymer, poly(ethylene oxide) based thickeners, sodium carbomer,and mixtures thereof.

Compositions of the present invention can optionally further compriseany additive or auxiliary agents usually used in the field(s) underconsideration. For example, dispersants such as poly(12-hydroxystearicacid), antioxidants, essential oils, sunscreens, preserving agents,fragrances, fillers, neutralizing agents, pH adjusters, cosmetic anddermatological active agents such as, for example, emollients, vitamins,essential fatty acids, surfactants, silicone elastomers, pastycompounds, viscosity increasing agents such as waxes orliposoluble/lipodispersible polymers, and mixtures thereof can be added.A non-exhaustive listing of such ingredients can be found in U.S. patentapplication publication no. 2004/0170586, the entire contents of whichare hereby incorporated by reference. Further examples of suitableadditional components can be found in the other references which havebeen incorporated by reference in this application. Still furtherexamples of such additional ingredients may be found in theInternational Cosmetic Ingredient Dictionary and Handbook (9^(th) ed.2002).

In the event that water is employed in the composition of the presentinvention, an embodiment of the composition of the present invention mayinclude an auxiliary ingredient chosen from at least one surfactant. Thesurfactant may be chosen from anionic, nonionic, amphoteric, cationic,and zwitterionic surfactants.

Preferably, the at least one surfactant may be employed in thecompositions of the present invention in an amount of from about 0.1% toabout 10% by weight, more preferably, from about 1% to about 7.5% byweight, and more preferably, from about 1.5% to about 5% by weight withrespect to the total weight of the composition, including all ranges andsubranges therebetween.

In the event that the composition of the present invention includeswater, the composition may comprise water in an amount of from about 1%to about 75% water, more preferably from about 5% to about 65% water,and more preferably from about 15% to about 50% water by weight withrespect to the total weight of the composition, including all ranges andsubranges therebetween.

According to other preferred embodiments, compositions of the presentinvention comprising water can include compositions in the form of asolid, a semi-solid or a cream such as a lipstick or a stick foundationor a cream foundation. Such compositions can comprise from between about5 to about 65%, preferably from about 10 to about 50%, more preferablyfrom about 15 to about 25% water by weight with respect to the totalweight of the composition, including all ranges and subrangestherebetween.

In one preferred embodiment of the present invention, the compositionsof the present invention are substantially free of silicone oils (i.e.,contain less than about 0.5% silicone oils). In another embodiment, thecompositions are substantially free of non-silicone oils (i.e., containless than about 0.5% non-silicone oils). In another embodiment, thecompositions are substantially free of non-volatile oils (i.e., containless than about 0.5% non-volatile oils).

Another preferred embodiment of the present invention is an emulsionwhich is substantially free of surfactant (that is, less than 3% ofsurfactant), essentially free of surfactant (that is, less than 2%surfactant), or free of surfactant (that is, less than 0.5% surfactant).

Another particularly preferred embodiment of the present invention is acomposition which contains so little elastomer that the presence of suchan elastomer does not affect the cosmetic properties of the composition.Preferably, the compositions are substantially free of such elastomers(i.e., contain less than about 0.5% elastomer), essentially free of suchelastomers (i.e., contain less than about 0.25% elastomer) or free ofsuch elastomer (i.e., contain no elastomer).

According to some embodiments of the present invention, the compositionsof the present invention are anhydrous. By “anhydrous,” it is meant thatthe composition contains substantially no water (that is, less thanabout 5% by weight of the composition of water).

According to other embodiments of the present invention, the compositionis an emulsion wherein the alkoxysilane having at least one solubilizingfunctional group and at least one amino substituent is present in thewater or an aqueous carrier or in both the oil carrier and in the wateror aqueous carrier.

Compositions of the present invention may further comprise a desiredagent such as a cosmetically active agent chosen from colorants.

In some embodiments, when water is present in the composition of thepresent invention, hyaluronic acid is additionally present in the wateror aqueous carrier. In other embodiments, a surfactant is additionallypresent in the water or aqueous carrier.

According to other preferred embodiments, cosmetic and personal carecompositions and methods of treating, caring for and/or making up orenhancing the appearance of keratinous material by applying suchcompositions to the keratinous material in an amount sufficient totreat, care for and/or enhance the appearance of the keratinous materialare provided. In accordance with these preceding preferred embodiments,the compositions of the present invention comprising at least one polarmodified polymer and at least one alkoxysilane having at least onesolubilizing functional group and at least one amino substituent areapplied topically to the desired area of the keratin material in anamount sufficient to treat, care for and/or enhance the appearance ofthe keratinous material. The compositions may be applied to the desiredarea as needed, preferably once or twice daily, more preferably oncedaily and then preferably allowed to dry before subjecting to contactsuch as with clothing or other objects (for example, a glass or atopcoat). Preferably, the composition is allowed to dry for about 1minute or less, more preferably for about 45 seconds or less. Thecomposition is preferably applied to the desired area that is dry or hasbeen dried prior to application, or to which a basecoat has beenpreviously applied.

According to a preferred embodiment of the present invention,compositions having improved cosmetic properties such as, for example,improved waterproof characteristics, improved feel upon application (forexample, texture, reduced drag or tackiness), increased anti-smudgingproperties, shine/color characteristics and/or increased long wearproperties are provided.

In some embodiments of the present invention, depending on the levels ofthe alkoxysilane having at least one solubilizing functional group andat least one amino substituent and/or of the polar modified polymer,compositions with varying viscosity and texture characteristics such asa unique bouncy gel texture or a creamy texture or a soft and smoothtexture are provided.

According to other embodiments of the present invention, methods ofimproving the anti-smudging, waterproof, transfer-resistance and/or longwear properties of a composition, comprising adding at least one polarmodified polymer and at least one alkoxysilane having at least onesolubilizing functional group and at least one amino substituent to thecomposition are provided. In accordance with this embodiment, the atleast one polar modified polymer and the at least one alkoxysilanehaving at least one solubilizing functional group and at least one aminosubstituent are present in amounts sufficient to achieve the desiredresult.

Unless otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective measurements. The following examples are intended toillustrate the invention without limiting the scope as a result. Thepercentages are given on a weight basis.

EXAMPLES Anhydrous Compositions (1-3)

Comparative Inventive Inventive Phase Chemical Name Example 1 Example 2Example 3 A1 Isododecane QS QS QS A1 Octododecanyl 20 20 20 PentanoateA1 Polyalkylene/Maleic 20 20 20 Anhydride Copolymer* (PPMA) A2Aminopropyl 0 0.5 1 Triethoxysilane (APTES) TOTAL 100 100 100 (*)PP207is a linear polypropylene-ethylene-maleic anhydride copolymer waxcommercially available from Clariant under the tradename LICOCARE PP207LP 3349.

Procedure

For each composition, all ingredients in Phase A1 were added to asuitable size metal container. The contents were heated to 85 Celsiusdegrees or until all solids had melted.

All ingredients indicated in phase A2 were added to the metal containerin a drop-wise fashion.

Contents were mixed at 80-85 Celsius degrees for 1 hour.

Contents were cooled to 25 Celsius degree while mixing.

Comparative Example 1 contained Polyalkylene/Maleic Anhydride Copolymer(PPMA, PP207) as the polar modified polymer (control). InventiveExamples 2 and 3 contained PPMA and aminopropyl triethoxysilane (APTES)as the alkoxysilane having at least one solubilizing functional groupand amino substituent with an amine group.

Comparing with the control (Comparative Example 1), it was found thatInventive Example 2 (PPMA+APTES) formed a viscous liquid that had a highaffinity to keratinous substrates. By increasing the concentration ofAPTES (Inventive Example 3), a bouncy gel was formed. With the viscousliquid, the film was easily spreadable and shiny, while the bouncy gelprovided a unique texture.

Emulsion Compositions: PPMA in Oil Phase and APTES in Water PhaseExample 4-6

Comparative Inventive Inventive Phase Chemical Name Example 4 Example 5Example 6 A Isododecane QS QS QS A Octododecanyl 20 20 20 Pentanoate APolyalkylene/Maleic 20 20 20 Anhydride Copolymer* (PPMA) B Water 25 2525 B Aminopropyl 0 0.25 1 Triethoxysilane (APTES) TOTAL 100 100 100(*)PP207 is a linear polypropylene-ethylene-maleic anhydride copolymerwax commercially available from Clariant under the tradename LICOCAREPP207 LP 3349.

Procedure

For each composition, all ingredients in Phase A were added to asuitable size metal container. The contents were heated to 85 Celsiusdegrees or until all solids had melted.

All ingredients indicated in phase B were added to a suitable size sidecontainer B, and mixed until uniform. The contents were also heated to85 Celsius degrees.

When both containers were at their proper temperatures, side container Bwas slowly added to main container A while mixing at high speed.

Contents were mixed at 80-85 Celsius degrees for 1 hour.

Contents were cooled to 25 Celsius degrees while mixing.

Comparative Example 4 contained PPMA and distilled water (control).Invention Examples 5 and 6 contained PPMA, and APTES in water.

Comparing with the control (Comparative Example 4), it was found thatInventive Example 5 (PPMA+Water+APTES) formed a cream that had a highaffinity to keratinous substrates and did not undergo phase separation.By increasing the concentration of APTES (Inventive Example 6), a bouncygel with high affinity to keratinous substrates was formed. While thecream provided a film that was easily spreadable on keratinoussubstrates, and was smooth, soft and shiny, the bouncy gel provided aunique texture. Increasing the APTES concentration also caused theemulsion droplet size to decrease, as observed by optical microscopy.

Emulsion Compositions with sodium hyaluronate: PPMA in oil phase andAPTES+HA in water phase (Examples 7-10)

Inventive Inventive Inventive Inventive Phase Chemical Name Example 7Example 8 Example 9 Example 10 A Polyalkylene/ 7.00 7.00 7.00 7.00Maleic Anhydride Copolymer* (PPMA) A Isododecane 43.00 43.00 43.00 43.00B Water QS QS QS QS B Sodium 0.50 0.50 0.50 0.50 Hyaluronate (HA) BAminopropyl 0.58 1.67 3.33 6.67 Triethoxysilane (APTES) (*)PP207 is alinear polypropylene-ethylene-maleic anhydride copolymer waxcommercially available from Clariant under the tradename LICOCARE PP207LP 3349.

Procedure

For each composition, all ingredients in Phase A were added to asuitable size metal container. The contents were heated to 85 Celsiusdegrees or until all solids had melted.

All ingredients indicated in phase B were added to a suitable size sidecontainer B, and mixed until uniform. The contents were also heated to85 Celsius degrees for 8 hrs.

When both containers were at their proper temperatures, side container Bwas slowly added to main container A while mixing at high speed.

Contents were mixed at 80-85 Celsius degrees for 1 hour.

Contents were cooled to 25 Celsius degree while mixing.

Example 7 was a light cream with well defined emulsion droplet size.Example 8 was a thicker cream with smaller emulsion droplet size.Example 9 exhibited a gelling texture and strong film formation. Example10 exhibited a bouncy gelling texture and enhanced film formation.

Emulsion Compositions: PPMA+APTES in Oil Phase and HA in Water PhaseExamples 11-13

Comparative Inventive Inventive Phase Chemical Name Example 11 Example12 Example 13 A Water 50.00 50.00 50.00 A SODIUM 0.50 0.50 0.50HYALURONATE (HA) B Aminopropyl 0.00 0.25 0.50 Triethoxysilane (APTES) BIsododecane QS QS QS B Polyalkylene/Maleic 7.00 7.00 7.00 AnhydrideCopolymer* (PPMA) (*)PP207 is a linear polypropylene-ethylene-maleicanhydride copolymer wax commercially available from Clariant under thetradename LICOCARE PP207 LP 3349.

Procedure

For each composition, all ingredients in Phase A were added to asuitable size metal container. The contents were heated to 85 Celsiusdegrees or until all solids had melted.

All ingredients indicated in phase B were added to a suitable size sidecontainer B, and mixed until uniform. The contents were also heated to85 Celsius degrees.

When both containers were at their proper temperatures, side container Bwas slowly added to main container A while mixing at high speed.

Contents were mixed at 80-85 Celsius degrees for 1 hour.

Contents were cooled to 25 Celsius degree while mixing.

Comparative Example 11 showed clear separation once mixing was stopped.Inventive Example 12 formed a smooth cream that has good spreadabilityand film forming properties. Inventive Example 13 formed a semi-solidgel that was bouncy and had very good film forming properties and waterresistance.

Emulsion Compositions: PPMA+APTES in Oil Phase and APTES+HA in WaterPhase Examples 14-17

Inventive Inventive Inventive Inventive Example Example Example PhaseChemical Name Example 14 15 16 17 A Water 50.00 50.00 50.00 50.00 ASODIUM 0.50 0.50 0.50 0.50 HYALURONATE (HA) A APTES 0.05 0.13 0.38 0.75B isododecane QS QS QS QS B Polyalkylene/ 7.00 7.00 7.00 7.00 MaleicAnhydride Copolymer* (PPMA) B APTES 0.05 0.13 0.38 0.75 (*)PP207 is alinear polypropylene-ethylene-maleic anhydride copolymer waxcommercially available from Clariant under the tradename LICOCARE PP207LP 3349.

Procedure

For each composition, all ingredients in Phase A were added to asuitable size metal container. The contents were heated to 85 Celsiusdegrees or until all solids had melted.

All ingredients indicated in phase B were added to a suitable size sidecontainer B, and mixed until uniform. The contents were also heated to85 Celsius degrees for 8 hrs.

When both containers were at their proper temperatures, side container Bwas slowly added to main container A while mixing at high speed.

Contents were mixed at 80-85 Celsius degrees for 1 hour.

Contents were cooled to 25 Celsius degree while mixing.

Inventive Example 14 was a light cream with well defined emulsiondroplet size. Inventive Example 15 was a thicker cream with smalleremulsion droplet size. Inventive Example 16 exhibited a gelling textureand strong film formation. Inventive Example 17 exhibited a bouncygelling texture and enhanced film formation.

1. (canceled)
 2. A method for preparing an emulsion compositioncomprising combining (a) at least one aqueous phase comprising at leastone alkoxysilane having at least one solubilizing functional group andat least one amino substituent; and (b) at least one oil phasecomprising at least one polar modified polymer to form an emulsioncomposition, wherein a reaction product comprising the at least onepolar modified polymer and the at least one alkoxysilane having at leastone solubilizing functional group and at least one amino substituent isformed during preparation of the emulsion composition.
 3. The method ofclaim 2, wherein the oil phase comprises at least one volatile oil. 4.The method of claim 2, wherein the oil phase comprises at least onenon-volatile oil.
 5. The method of claim 2, wherein the at least onealkoxysilane having at least one solubilizing functional group and atleast one amino substituent is 3-aminopropyltriethoxysilane.
 6. Themethod of claim 2, wherein the polar modified polymer is an oil-solublepolar modified polymer.
 7. The method of claim 2, wherein the polarmodified polymer is an oil-soluble high carbon polar modified polymer.8. The method of claim 5, wherein the polar modified polymer is anoil-soluble polar modified polymer.
 9. The method of claim 5, whereinthe polar modified polymer is an oil-soluble high carbon polar modifiedpolymer.
 10. The method of claim 2, wherein the polar modified polymeris a polypropylene and/or polyethylene-maleic anhydride modified wax.11. The method of claim 5, wherein the polar modified polymer is apolypropylene and/or polyethylene-maleic anhydride modified wax.
 12. Themethod of claim 2, wherein the at least one aqueous phase comprises fromabout 5 to about 65% by weight water, based on the weight of thecomposition.
 13. The method of claim 2, wherein the at least onealkoxysilane having at least one solubilizing functional group and atleast one amino substituent is present in an amount of from about 0.01to about 10% by weight, based on the total weight of the composition.14. The method of claim 5, wherein the at least one alkoxysilane havingat least one solubilizing functional group and at least one aminosubstituent is present in an amount of from about 0.01 to about 10% byweight, based on the total weight of the composition.
 15. The method ofclaim 11, wherein the at least one alkoxysilane having at least onesolubilizing functional group and at least one amino substituent ispresent in an amount of from about 0.01 to about 10% by weight, based onthe total weight of the composition.
 16. The method of claim 2, whereinthe polar modified polymer is present in an amount of from about 1% toabout 30% by weight, based on the weight of the composition.
 17. Themethod of claim 6, wherein the polar modified polymer is present in anamount of from about 1% to about 30% by weight, based on the weight ofthe composition.
 18. The method of claim 7, wherein the polar modifiedpolymer is present in an amount of from about 1% to about 30% by weight,based on the weight of the composition.
 19. The method of claim 10,wherein the polar modified polymer is present in an amount of from about1% to about 30% by weight, based on the weight of the composition. 20.The method of claim 11, wherein the polar modified polymer is present inan amount of from about 1% to about 30% by weight, based on the weightof the composition.
 21. The method of claim 2, wherein the compositionfurther comprises at least one colorant.